A new hydrogenated aluminophosphate oxynitride (ALPON) obtained by nitridation of AlPO4 can be used as a support to prepare a polyfunctional catalyst with both basic and metallic sites. Ni/ALPON catalyst was effective for the low-pressure one-step methyl isobutyl ketone (MIBK) synthesis from acetone. The selectivity of the process depended on the temperature and time-on-stream of the hydrogen reduction treatment suggesting that selective MIBK production is achieved by a fine balance between basic and metallic sites.